CN104667839A - Colloidal dispersions of compounds of cerium and at least one of zirconium, rare earths, titanium and/or tin, dispersible solid based on said compound, and preparation methods - Google Patents
Colloidal dispersions of compounds of cerium and at least one of zirconium, rare earths, titanium and/or tin, dispersible solid based on said compound, and preparation methods Download PDFInfo
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- CN104667839A CN104667839A CN201510033691.XA CN201510033691A CN104667839A CN 104667839 A CN104667839 A CN 104667839A CN 201510033691 A CN201510033691 A CN 201510033691A CN 104667839 A CN104667839 A CN 104667839A
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Abstract
Colloidal dispersions, in a continuous phase, contain a compound of cerium and another element M selected from among zirconium, rare earths (Ln) other than cerium, titanium and tin, wherein such compound is in the form of a mixed oxide in which the cerium and the element M are in solid solution; the cerium is in the form of cerium III in an amount expressed in cerium III/total cerium atomic ratio ranging between 0.005 and 0.06 and the dispersion is produced by forming a liquid medium comprising cerium salts, in particular of cerium III, and the element M, contacting the medium with a base to provide a pH of not less than 9, separating and washing the resulting precipitate and peptizing same by treating with an acid whereby the dispersion is obtained. The method further includes a step of washing after separating the precipitate or after the peptizing.
Description
Present patent application is the divisional application based on application number is 200680016321.4, denomination of invention is " colloidal dispersion of the compound of the other element of cerium and selected among zirconium, rare earth metal, titanium and tin, based on the dispersible solid of this compound and preparation method ", the applying date is the Chinese patent application on April 18th, 2006.
Technical field
The present invention relates to the colloidal dispersion of the compound of other element M of at least one of cerium and selected among zirconium, rare earth metal, titanium and tin, dispersible solid and preparation method thereof based on this compound.
Background technology
Based on cerium and the compound as the oxide of the other element of zirconium or rare earth metal and so on, there is very large benefit.Due to their high oxygen storage power and their heat endurance, they can be used in catalytic field.They also can be used as the reagent of antiultraviolet or are used as pigment.
In addition, industrially extremely need nanoparticle form, be more particularly this compound of colloidal dispersion form.But, the preparation of the dispersion of this compound is also not easy, and need the method for relative complex.In addition, known method can not obtain highly crystalline form, is particularly the dispersion of the compound of solid solution thereof at least partly.In fact, in some applications, particularly in catalytic field, finding the product existed with solid solution thereof, these solid solution produces the character improved.Therefore this dispersion of solid solution is needed.
Summary of the invention
Therefore object of the present invention is to provide these colloidal dispersions and produces its method.
With this end in view, dispersion of the present invention is cerium and selected among zirconium, the colloidal dispersion of compound in continuous phase of other element M of at least one of rare earth metal (Ln), titanium and tin except cerium, it is characterized in that, this compound is the form of mixed oxide, wherein cerium and element M are pure solid solution thereof, and it is characterized in that this compound comprises the cerium that the amount represented with the atomic ratio of cerium (III)/total cerium is cerium (III) form of 0.005 to 0.06.
In addition, the invention still further relates to the method preparing above-mentioned dispersion, it comprises the following steps:
-forming the liquid medium comprising the salt of cerium and at least one element M, this cerium salt is the salt of cerium (IV) and cerium (III);
-this medium is contacted with alkali with the pH value obtaining at least 9, obtain sediment thus;
-described sediment is separated with medium;
-wash this sediment;
-by making this sediment peptization with acid treatment, obtain dispersion thus; At least one washing step after the method is included in sediment separating step in addition or after peptization step.
Said method comprises relatively less number of steps and can directly obtain required dispersion by simple chemical operation, and this is applicable in the different multiple dispersion of the element properties of mixed oxide.
Accompanying drawing explanation
Reading following explanation and for its various concrete of illustration but after non-limiting example and accompanying drawing, further feature of the present invention, details and advantage become more fully clear, in the accompanying drawings:
-Fig. 1 is the X-ray diagram of the compound based on cerium and titanium from dispersion of the present invention;
-Fig. 2 is the X-ray diagram of the compound based on cerium and zirconium from dispersion of the present invention.
Detailed description of the invention
For this description hereafter, term " colloidal dispersion of the compound of cerium and other element M or colloidal sol " refers to by the fine solid particles of the colloid size of this compound, namely size is generally 1 nanometer to 100 nanometer, particularly any system of the particle formation of 2 nanometer to 50 nanometers.These particles are based on the oxide of the cerium be suspended in liquid continuous phase and other element M, and described particle comprises the ion of bonding or absorption as counter ion counterionsl gegenions, such as acetate, nitrate anion, chlorine root or ammonium.It should be noted that, in this kind of dispersion, cerium and other element M can exist completely in colloidal form, or exist with ion or polyion form and colloidal form simultaneously.
Liquid continuous phase is generally in the present case containing aqueous phase, more especially water.
In addition, in this manual, term " rare earth metal " is understood to mean and is selected from the element that yttrium and period of element atom ordinal number are the element of 57 to 71 (comprising 57 and 71).Unless otherwise specified, term " trivalent rare earth metals " be understood to mean can only with trivalent form exist rare earth metal.
Finally, specify, unless otherwise specified, given number range comprises boundary value.
One of feature of dispersion of the present invention is, above-claimed cpd is mixed oxide (Ce, M) O
2form, wherein cerium and element M are solid solution thereof.This is understood to mean one of these elements (normally element M) and is fully introduced in the lattice of the oxide of other matrix forming element (such as cerium).This introducing by after washing, particularly passes through ultrafiltration or pass through ultracentrifugation, and the x-ray diffraction technique on colloid dry at the temperature of 60 DEG C can confirm.The crystal structure that and the cell parameter corresponding with the oxide (normally cerium oxide) of matrix forming element of showing X-ray diagram to exist more or less departs from relative to the pure-oxide of this first matrix forming element, therefore this confirm to introduce other element in the lattice of the oxide of the first element.Such as, when the solid solution of element M in cerium oxide, X-ray diagram demonstrates just as crystalline silica cerium CeO
2the same fluorite type crystal structure, but how many its cell parameters deviate from pure ceria, shows thus to introduce element M in the lattice of cerium oxide.
This solid solution is pure, and that is, a kind of all amounts of element are all solid-solution in other element, and such as, all elements M is solid-solution in cerium oxide.In this case, X-ray diagram only shows the existence of solid solution and does not contain the line corresponding with the oxide type (oxide of such as element M) of the element beyond matrix forming element.
As mentioned above, element M selected among zirconium, rare earth metal (Ln), titanium and tin except cerium, as hereinafter finding out from this description, these elements can exist as mixture certainly.
Another feature of dispersion of the present invention is that cerium exists with cerium (III) form.The amount of the cerium (III) represented with the atomic ratio of cerium (III)/total cerium is for 0.005 to 0.06.More particularly, this amount can be 0.005 to 0.05, particularly 0.005 to 0.03.
It should be noted that, cerium (III) can exist with the form be adsorbed on cerium compound particle surface or in the crystal structure cell of this compound as cation in compound.Certainly, these forms can coexist.
The existence of the cerium (III) of dissolved form can be confirmed by stoichiometric determination method.Therefore the current potential calibrating analytical technology by using the potassium ferricyanide cerium (III) to be oxidized to cerium (IV) in potash medium can be used.Cerium (III) can be confirmed by the mensuration of the isoelectric point of colloidal dispersion in the existence of particle surface.This mensuration is carried out in known manner by the change of measuring dispersion zeta potential.When by by dispersion pH value from acidic value become alkalescence value measure this potential change time, this current potential is from the occasion of becoming negative value, and current potential is in the transition formation isoelectric point of 0 value.With the Compound Phase ratio only containing cerium (IV), cerium (III) improves the value of isoelectric point in the existence on surface.
Now according to the character of cerium compound, more specifically according to the character more detailed description various alternative form of the present invention of element M.It should be noted that at this, the chemical formula provided in the description of these alternative forms below corresponded to by forming of obtaining the chemical analysis of colloid, this colloid is by reclaiming 50000 revs/min of lower ultracentrifugations 6 hours or after washing dispersion, and this washing is by ultrafiltration or by carrying out with water (a 1 volume integral prose style free from parallelism: the 10 volume water) dialysis of at least 10 equivalent volumes.
According to the first alternative form, element M is zirconium.More particularly, when this alternative form, this compound can meet formula (1) Ce
1-xzr
xo
2, wherein x is less than 1 and at least equals 0.01, preferably at least equals 0.02.
According to another alternative form, element M is the combination of zirconium and tin.More particularly, when this alternative form, this compound can meet following formula (2) Ce
1-x-yzr
xsn
yo
2, wherein eligible 0.05≤x≤0.95 of x+y<1, x, and y at least equals 0.01, selects high y value really to obtain solid solution.Preferably, eligible 0.20≤x≤0.8 of x, more preferably eligible 0.40≤x≤0.60.Preferably, y at least equals 0.05, and more preferably y at least equals 0.2.Preferably, y equals 0.4 at most, more preferably equals 0.25 at most.
According to the 3rd alternative form, element M is the combination of zirconium and at least one rare earth metal Ln, and it is the situation of trivalent rare earth metals that the present invention is suitable for wherein rare earth metal especially.Rare earth metal can particularly lanthanum, gadolinium, terbium, praseodymium or neodymium.More particularly, when the 3rd alternative form, this compound can meet formula (3) Ce
1-x-yzr
xln
yo
2, wherein eligible 0.05≤x≤0.95 of x+y<1, x, and y at least equals 0.01, selects high y value really to obtain solid solution.Preferably, eligible 0.20≤x≤0.8 of x, more preferably eligible 0.40≤x≤0.60.Preferably, y at least equals 0.02, and more preferably y at least equals 0.04.Preferably, y equals 0.05 at most, more preferably equals 0.03 at most.When this alternative form, element M can be the combination of at least two kinds of rare earth metals, and wherein at least one is praseodymium.Finally, can point out, when M be the optional terbium that combine with other rare earth metal or praseodymium, these elements can with Tb (III) and Pr (III) form and Tb (IV) and the existence of Pr (IV) form.
According to an alternative form again, element M is the combination of zirconium, tin and at least one rare earth metal Ln.Equally, the present invention is particularly well suited to the situation that rare earth metal is trivalent rare earth metals very much, and rare earth metal can particularly lanthanum, gadolinium, terbium, praseodymium or neodymium.More particularly, when this alternative form, this compound can meet formula (4) Ce
1-x-y-zzr
xsn
yln
zo
2, wherein eligible 0.05≤x≤0.95 of x+y+z<1, x, y at least equals 0.01, and z at least equals 0.01.Preferably, eligible 0.20≤x≤0.8 of x, and y at least equals 0.10, more preferably, eligible 0.40≤x≤0.60 of x and y at least equals 0.2.Select high y and z value really to obtain solid solution.Preferably, y equals 0.4 at most, more preferably equals 0.25 at most; In addition, preferably, z equals 0.05 at most, more preferably equals 0.03 at most.
The compound of dispersion of the present invention also can be M is the compound that rare earth metal or rare earth metal combine.Equally, the present invention is particularly well suited to the situation that rare earth metal is trivalent rare earth metals very much.Rare earth metal can particularly lanthanum, gadolinium, terbium, praseodymium or neodymium.This compound particularly meets following formula (5) Ce thereupon
1-xln
xo
2, wherein x equals 0.15 at most and at least equals 0.01, preferably at least equals 0.02, more preferably at least equals 0.04.Preferably, x equals 0.10 at most, more preferably equals 0.05 at most.Rare earth metal can be Ln (III) form at least partly, exists in crystal structure cell or with the form be adsorbed on the particle surface of cerium compound.When praseodymium, this element can exist with Pr (III) and Pr (IV) form, and in the same circumstances, x particularly at least equals 0.04, is more particularly 0.03 to 0.08.
According to an alternative form more of the present invention, this compound is formula (6) Ce
1-xti
xo
2mixed oxide, wherein x equals 0.6 at most and at least equals 0.01, preferably at least equals 0.05, more preferably at least equals 0.2.Preferably, x equals 0.5 at most.
The particle performance forming the compound of dispersion goes out fine and narrow size distribution.This is because they have preferably maximum 10 nanometers recorded by its average diameter, the more especially size of 2 to 8 nanometers.This size on the carbon film of load on copper grid, pre-dry sample measures conventionally by Transmission electron microscopy (TEM) and is the mean value measured for 50 times.
In addition, these particles are fully separated.Low temperature-TEM technology can be used to measure the coherent condition of particle.Can be observed by Transmission electron microscopy and keep freezing sample in its crude media (it can be such as water).
For aqueous specimen, carry out freezing in liquid ethane on the film of about 50 to 100 nanometers of thickness.
The dispersity of particle is fully kept by low temperature-TEM and represents the existence in true medium.In this case, low temperature-TEM confirms the abundant separation outward appearance of particle.
Dispersion of the present invention usually show can be 0.5 to 6 pH value.
Dispersion of the present invention shows at least 0.1M usually, preferably at least 0.25M, is advantageously greater than the mixed oxidization substrate concentration of 1M.
Other specific embodiments of present description dispersion of the present invention.
A kind of concrete form is corresponding to the dispersion with alkaline ph values.According to this form, the compound of cerium and other element M of at least one exists with the form comprising the particle of citrate anion in addition, and these anion are attracted on particle surface.Mol ratio r=citric acid/mixed oxide is generally 0.1 to 0.6, and preferably 0.2 to 0.45.For this embodiment, the pH value of dispersion is at least 7, preferably at least 8.
Another specific embodiments corresponds to functionalized dispersion.In this case, the compound of cerium and other element M of at least one comprises the form existence of the particle of difunctional compound with surface, this difunctional compound comprises the functional group R of amine, sulfuric ester, phenyl, alkyl ethoxy or succinic acid ester type
1with the functional group R of carboxylic acid, dicarboxylic acids, phosphoric acid, phosphonic acids or sulfonic acid type
2, functional group R
1and R
2pass through-(CH
2)
xthe organic chain of-type separates, and x preferably equals 6 at most.This difunctional compound can be considered to by functional group R
2with the solvay-type between the cerium or M of the existence of colloidal particle surface interacts and is bonded on the surface.Mol ratio r '=difunctional compound/mixed oxide mostly is 0.6 most usually, and preferably maximum 0.4, more preferably maximum 0.2.
Difunctional compound can be selected from aliphatic amino acid, such as aminocaproic acid, amination sulfonic acid, such as aminoethane sulfonic acid, or alkyl polyoxyethylene ether phosphate.
Finally, it should be noted that, colloidal dispersion of the present invention is stable especially, that is, through may not observing the time more than 1 year by sedimentation or the separation caused that is separated.
The preparation method of present description dispersion of the present invention.
As mentioned above, the method comprises the first step being formed and comprise the liquid medium of the salt of cerium salt and at least one element M, and this cerium salt is the salt of cerium (IV) and cerium (III).Cerium (III) salt represented by the mol ratio of cerium (III)/total cerium (Ce (III)+Ce (IV)) and the ratio of cerium (IV) salt are generally at least 2% and maximum 20%, preferably 2% to 10%, this ratio is selected according to cerium (III) content required in the colloidal dispersion that will prepare.Liquid medium is water normally, and salt is introduced usually in the form of a solution.
Salt can be inorganic or organic acid salt, such as sulfate, nitrate, chloride or acetate type, it being understood that initial medium must comprise at least one cerium (IV) salt.Ceric nitrate ammonium salt solution particularly can be used as cerium (IV) solution, add cerium (III) with cerous nitrate or cerous acetate (III) or cerous chloride form wherein.Also can use by corroding CeO with nitric acid
2and the ceric nitrate solution obtained, in this solution, add Ce (III).Can advantageously use obtained by electrolysis and comprise the ceric nitrate solution of Ce (III).Ti (IV) solution can be TiOCl
2.The solution of Zr (IV) can be ZrOCl
2or ZrO (NO
3)
2solution.SnCl can be used
45H
2o is as pink salt.Rare earth metal Ln introduces with Ln (III) salt such as nitrate salts usually.
The second step of the method is that the medium making as above to be formed contacts with alkali.
The product of hydroxide type can be used especially as alkali.Alkali metal hydroxide, alkaline earth metal hydroxide and ammoniacal liquor can be mentioned.Also secondary amine, tertiary amine or quaternary amine can be used.But just reduce with regard to the danger of being polluted by alkali metal or alkaline earth metal cation, amine and ammonia can be preferred.
The interpolation of alkali is instantaneous or carry out gradually obtaining at least 9, and preferably at least 9.5, the more preferably PH values of at least 10.The interpolation of alkali causes forming sediment.
After the interpolation of alkali, the time usual for medium slaking at ambient temperature can not waited for such as 10 minutes to 1 hour.
Can any known method be passed through, such as, be separated with liquid medium by the centrifugal sediment that makes.
The sediment obtained by reaction can be washed subsequently.Then this washing can be undertaken by making solid be separated (such as by centrifugal) with liquid medium after agitation by making sediment get back in water.If necessary, this operation can repeat for several times.Usually, carry out this washing to obtain washing slurry, namely sediment is resuspended in water wherein, and its pH value is maximum 8.75, and preferably maximum 8, advantageously maximum 7.
The final step of the method is the sedimentary peptization step as above obtained.This peptization is by carrying out with acid treatment sediment.This process is undertaken by disperseing sediment also to stir the medium formed thus in an acidic solution usually.Such as can use nitric acid, hydrochloric acid or acetic acid.Acetic acid can be advantageously used in the compound dispersion obtaining high-load trivalent rare earth metals.Peptization, usually in environment temperature to 90 DEG C, preferably carries out at ambient temperature.The amount of acid used makes H
+/ (Ce+M) mol ratio usually maximum 1.5, preferably maximum 1.25, more preferably maximum 1.At the end of peptization, directly and obtain colloidal dispersion of the present invention without other intermediate steps.
Thus obtained dispersion can be washed by ultrafiltration or by dialysis.It may be the element M of ionic species that this washing can be removed.
It should be noted that, method of the present invention comprises at least one washing step, and this washing can be carried out under the condition just described, and namely carries out for sediment or dispersion or the two.
Particle is comprised to the above-mentioned specific embodiments of citrate anion on surface, its preparation method is the type just described, but it is implemented by the step contacted with citric acid.More specifically, citric acid can add in the dispersion obtained after peptization, such as, with citric acid monohydrate powder type.Citric acid under agitation dissolves subsequently.In the scope of the value that citric acid/mixed oxide mol ratio provides above, namely usual 0.1 to 0.6.Gained medium can be placed 30 minutes to 24 hours at ambient temperature.
Subsequently, add aqueous slkali gradually, this alkali for above to type identical described in settling step, to obtain at least 7, the preferably required pH value of at least 8.More specifically, this interpolation can be carried out at ambient temperature between 10 minutes to 2 hours.
Equally, in order to obtain the functionalized dispersion according to above-mentioned embodiment, in the dispersion obtained after peptization, difunctional compound is added.
The invention still further relates to dispersible solid, namely can produce the solid of colloidal dispersion of the present invention.
This solid exists with powder or paste form.It is based on the compound of other element M of at least one of cerium and selected among zirconium, rare earth metal (Ln), titanium and tin except cerium, and this compound is the form of mixed oxide, and wherein cerium and element M are solid solution thereof.Above about mixed oxide forms compound described in all the elements be also all applicable to this.When above-mentioned specific embodiments, the particle forming this solid comprises citrate anion or the difunctional compound of complex form from the teeth outwards.
This solid can pass through in a mild condition, and namely at maximum 80 DEG C, from dispersion, single vaporization water obtains.
This solids exhibit goes out redispersible, namely in liquid phase, can produce according to colloidal dispersion as above of the present invention when particularly suspending in water.
Dispersion of the present invention can be used in numerous applications.Catalysis can be mentioned, especially for automobile after-burning; In this case, in catalyst preparing, this dispersion is used.This dispersion also can for lubrication in pottery or in pigment manufacture; Wherein compound is the mixed oxide of cerium and praseodymium and to present red dispersion like this especially.Also can utilize the ultraviolet inhibition of this dispersion, such as, for the preparation of (such as acrylic acid or polycarbonate-type) thin polymer film or cosmetic composition, particularly prepare the breast frost of ultraviolet radiation preventing.Dispersion based on the mixed oxide of cerium and gadolinium can be used for preparing fuel cell material.Finally, they can be used as corrosion inhibiter and are used in substrate.
Provide embodiment now.
Embodiment 1
This embodiment relates to formula Ce
0.78ti
0.22o
2the preparation of colloidal dispersion of particle.
Ce will be passed through
3+the Ce with 1.425M of the electrolytic oxidation acquisition of solution
4+(the i.e. Ce of 50 mMs
4+) concentration, 0.11M Ce
3+the HNO of concentration and 0.7M
335 milliliters of ceric nitrate solution of concentration add Ti to
4+concentration is the 4.6M (Ti of 12.5 mMs
4+) 2.7 milliliters of TiOCl
2in solution.Volume is made into 500 milliliters.PH value is 1.3.
Instantaneously add 40 milliliters of 28%NH
3solution.PH value is 10.
The sediment of formation is leached and uses 4 × 1 liters of deionized water washings.The pH value of slurry is 7.5.
This operation is repeated twice (i.e. three operations altogether).
Sediment is resuspended in and comprises 7.2 grams of 68%HNO
3(H
+/ (Ce+Ti)=1.25, in solution by mol), and are made into 100 milliliters by volume.Ce+Zr concentration equals 0.625M.This mixture is stirred and spends the night.Obtain concerning naked eyes clarification colloidal dispersion.
List dispersions obtained characteristic below.
Use dialyser, wash dispersion by dialysis.Pour 80 milliliters of colloidal dispersions into dialysis bag and carry out dialysis in 500 milliliters of cylinders that deionized water is housed.Make dialysis carry out 24 hours, and water is changed 5 times.
The atomic ratio of Ce (III)/total Ce of 0.05 is recorded by the chemical analysis on washed colloidal dispersion.
The colloid that colloidal dispersion washed is thus measured by TEM is of a size of 4 nanometers.
Dry colloid by obtaining through the colloidal dispersion of dialysis 50 DEG C of evaporations carries out X-ray diffraction analysis.The diffracting diagram provided in Fig. 1 reveals monocrystalline specific line mutually, and with do not adding according to identical program the dry CeO that Ti makes
2diffraction pattern (the cell parameter that colloid produces
) compare and show slight displacement of the lines (cell parameter
), confirm the solid solution characteristic of particle thus.
Embodiment 2
This embodiment relates to formula Ce
0.94pr
0.06o
2the preparation of colloidal dispersion of particle.
By Pr
3+concentration is the 2.95M (Pr of 25 mMs
3+) 8.5 milliliters of Pr (NO
3)
3solution adds to and passes through Ce
3+the Ce with 1.425M of the electrolytic oxidation acquisition of solution
4+(the i.e. Ce of 100 mMs
4+) concentration, 0.11M Ce
3+the HNO of concentration and 0.7M
370 milliliters of ceric nitrate Ce (NO of concentration
3)
4in solution, and volume is made into 1000 milliliters.PH value is 1.3.Instantaneously add 80 milliliters of 28%NH
3solution; PH value is 10.
Sediment is used on a sintered glass funnel 4 × 1 liters of deionized water washings.The pH value of slurry is 7.5.
After filtration, by this product with comprising 11.6 gram of 68% nitric acid (125 mMs of H
+) solution with re-suspension, and volume is made into 250 milliliters.H
+/ (Ce+Pr) mol ratio equals 1.PH value is 1.1.Ce+Pr concentration equals 0.5M.This mixture is stirred and spends the night.
This colloidal dispersion is washed by dialysis as in Example 1.
Colloidal dispersion is concerning naked eyes being clarification and be red.
The atomic ratio of Ce (III)/total Ce of 0.03 is recorded by the chemical analysis on washed colloidal dispersion.
The colloid measured by TEM is of a size of 4 nanometers.
Dry colloid by obtaining through the colloidal dispersion of dialysis 50 DEG C of evaporations carries out X-ray diffraction analysis.This diffracting diagram reveals monocrystalline specific line, wherein cell parameter mutually
meet pure CeO
2parameter.Do not observe displacement of the lines by X-ray diffraction thus, this is due to Pr
3+the low concentration of adulterant causes.In any case the redness of colloid shows to define at CeO
2fluorite structure in be inserted with Pr
4+the solid solution of ion.
Embodiment 3
This embodiment relates to formula Ce
0.53zr
0.46o
2the preparation of colloidal dispersion of particle.
Ce will be passed through
3+the Ce with 1.425M of the electrolytic oxidation acquisition of solution
4+(the i.e. Ce of 62.5 mMs
4+) concentration, 0.11M Ce
3+the HNO of concentration and 0.7M
344 milliliters of ceric nitrate solution of concentration add Zr to
4+concentration is the 3.32M (Zr of 62.5 mMs
4+) 19 milliliters of ZrO (NO
3)
2in solution.Volume is made into 1000 milliliters.PH value is 1.06.
Instantaneously add 80 milliliters of 28%NH
3solution.PH value is 10.
The sediment of formation is leached and the 1 liter of deionized water washing of continuous 4 use.The pH value of slurry is 7.5.
This operation is repeated twice (i.e. three operations altogether).
Sediment is resuspended in and comprises 26.1 grams of 68%HNO
3(H
+/ Ce+Zr=0.75, in solution by mol), and is made into 600 milliliters by volume.Ce+Zr concentration equals 0.625M.This mixture is stirred and spends the night.Obtain the colloidal dispersion concerning clarification naked eyes.
List dispersions obtained characteristic below.
Then colloidal dispersion is washed by dialysis as in Example 1.
The colloid that colloidal dispersion washed is thus measured by TEM is of a size of 4 nanometers.
The Ce of 0.007 is measured by the chemical analysis in washed dispersion
3+/ Ce
total amountratio and chemical composition Ce
0.53zr
0.46o
2.
Measured by electrophoresis, measure and there is Ce on the surface at colloidal particle
3+time the distinctive isoelectric point equaling pH 9.
Dry colloid by obtaining through the colloidal dispersion of dialysis 50 DEG C of evaporations carries out X-ray diffraction analysis.The diffracting diagram provided in Fig. 2 reveals (Ce, Zr) O
2type monocrystalline is specific line mutually, and with do not adding according to identical program the dry CeO that Zr makes
2the diffraction pattern that colloid produces is compared and is shown slight displacement of the lines (cell parameter
), confirm the solid solution characteristic of particle thus.
Embodiment 4
This embodiment relates to formula Ce
0.38zr
0.37sn
0.24o
2the preparation of colloidal dispersion of particle.
Ce will be passed through
3+the Ce with 1.425M of the electrolytic oxidation acquisition of solution
4+(the i.e. Ce of 50 mMs
4+) concentration, 0.11M Ce
3+the HNO of concentration and 0.7M
335 milliliters of ceric nitrate solution of concentration, add Zr to
4+concentration is the 3.32M (Zr of 50 mMs
4+) 15 milliliters of ZrO (NO
3)
2in solution.Under agitation in the mixed solution of cerous nitrate and zirconium, dissolve 8.8 grams of SnCl
45H
2o (i.e. 25 mMs of Sn).Volume is made into 1000 milliliters.PH value is 1.2.
Instantaneously add 80 milliliters of 28%NH
3solution.PH value is 10.
The sediment of formation is leached and the 1 liter of deionized water washing of continuous 4 use.The pH value of slurry is 7.4.
Sediment is resuspended in and comprises 8.7 grams of 68%HNO
3(H
+/ Ce+Zr=0.75, in solution by mol), and is made into 200 milliliters by volume.Ce+Zr concentration equals 0.625M.This mixture is stirred and spends the night.Obtain the colloidal dispersion concerning clarification naked eyes.
Dispersion is washed as in Example 1 by dialysis.
The colloid that colloidal dispersion washed is thus measured by TEM is of a size of 4 nanometers.
The Ce of 0.0064 is measured by the chemical analysis in washed dispersion
3+/ Ce
total amountratio and chemical composition Ce
0.38zr
0.37sn
0.24o
2.
Dry colloid by obtaining through the colloidal dispersion of dialysis 50 DEG C of evaporations carries out X-ray diffraction analysis.This diffracting diagram reveals (Ce, Zr) O
2type monocrystalline is specific line mutually, and with do not adding according to identical program the dry CeO that Zr and Sn make
2the diffraction pattern that colloid produces is compared and is shown slight displacement of the lines (cell parameter
), confirm the solid solution characteristic of particle thus.
Embodiment 5
This embodiment relates to the formula Ce under alkaline ph values
0.53zr
0.46o
2the preparation of colloidal dispersion of particle.
6.9 grams of monohydrate potassiums (Mw=210 gram) to be added in 200 cubic centimetres of nondialyzed colloidal dispersions as made in foregoing embodiments 3 and to be diluted to the Ce of 60 grams per liters
0.53zr
0.46o
2concentration; Citrate/Ce
0.53zr
0.46o
2mol ratio is about 0.4.This mixture is stirred 60 minutes.After 60 minutes, in 15 minutes, add about 20%NH of 9 milliliters gradually
3solution.
The colloidal dispersion of pH value 8.5 is obtained after stirring is spent the night.
Embodiment 6
The dispersion of the embodiment 5 of the pH value 8.5 obtained passing through interpolation citrate is 45 DEG C of evaporations.Gained powder can disperse by adding water again.
Embodiment 7
This embodiment relates to formula Ce
0.9gd
0.1o
2the preparation of colloidal dispersion of particle.
By Gd
3+concentration is the 2.35M (Gd of 50 mMs
3+) 21 milliliters of Gd (NO
3)
3solution adds to and passes through Ce
3+the Ce with 1.425M of the electrolytic oxidation acquisition of solution
4+(the i.e. Ce of 200 mMs
4+) concentration, 0.11M Ce
3+the HNO of concentration and 0.7M
3140 milliliters of ceric nitrate Ce (NO of concentration
3)
4in solution, and volume is made into 2000 milliliters.PH value is 1.2.Instantaneously add 160 milliliters of 28%NH
3solution; PH value is 10.
Sediment is used on a sintered glass funnel 4 × 1 liters of deionized water washings.The pH value of slurry is 7.2.
After filtration, by this product solution with re-suspension comprising 15 gram of 100% acetic acid with 1.05 (262 mMs) density, and volume is made into 500 milliliters.Acetic acid/(Ce+Gd) mol ratio is 1.00.This mixture is stirred and spends the night.
Gained colloidal dispersion is washed by dialysis subsequently.Pour 80 milliliters of colloidal dispersions into dialysis bag and carry out dialysis in 500 milliliters of cylinders that deionized water is housed.
Make dialysis carry out 24 hours and water is changed 5 times.PH value is 5.
This colloidal dispersion is clarification concerning naked eyes, and colloid size is 4 nanometers, and is Ce by the chemical composition that quantitative determination process measures
0.9gd
0.1o
2.Due to the extremely low concentration of the adulterant of introducing, this diffracting diagram reveals and pure CeO
2identical monocrystalline is specific line, wherein cell parameter mutually
Embodiment 8
This embodiment relates to formula Ce
0.15zr
0.83la
0.02o
2the preparation of colloidal dispersion of particle.
Ce will be passed through
3+the Ce with 1.425M of the electrolytic oxidation acquisition of solution
4+(the i.e. Ce of 9.4 mMs
4+) concentration, 0.11M Ce
3+the HNO of concentration and 0.7M
36.6 milliliters of ceric nitrate solution of concentration add Zr to
4+concentration is the 3.32M (Zr of 50 mMs
4+) 15 milliliters of ZrO (NO
3)
2in solution.Add La subsequently
3+concentration is the 2.785M (La of 12.5 mMs
3+) 4.5 milliliters of La (NO
3)
3solution.With demineralized water, volume is made into 500 milliliters.PH value is 1.3.
Instantaneously add 40 milliliters of 28%NH
3solution.PH value is 10.
The sediment of formation is leached and the 1 liter of deionized water washing of continuous 4 use.The pH value of slurry is 7.5.
Sediment is resuspended in and comprises 7.2 grams of 68%HNO
3(H
+/ (Ce+Zr+La)=1.08, in solution by mol), and are made into 100 milliliters by volume.This mixture is stirred and spends the night.Obtain the colloidal dispersion concerning clarification naked eyes.
Dispersion is washed as in Example 1 by dialysis.
The colloid that colloidal dispersion washed is thus measured by TEM is of a size of 4 nanometers.
Dry colloid by obtaining through the colloidal dispersion of dialysis 50 DEG C of evaporations carries out X-ray diffraction analysis.This diffracting diagram reveals solid solution monocrystalline specific line mutually.
Claims (19)
1. the colloidal dispersion of compound in continuous phase of other element M of at least one of cerium and selected among zirconium, rare earth metal (Ln), titanium and tin except cerium, it is characterized in that, this compound is the form of mixed oxide, wherein cerium and element M are pure solid solution thereof, and this compound comprises the cerium that the amount represented with the atomic ratio of cerium (III)/total cerium is cerium (III) form of 0.005 to 0.06.
2. dispersion as claimed in claim 1, is characterized in that element M is the combination of zirconium, zirconium and tin, zirconium and the combination of at least one rare earth metal Ln or the combination of zirconium, tin and at least one rare earth metal Ln, and Ln can more especially trivalent rare earth metals.
3. dispersion as claimed in claim 2, is characterized in that this compound is formula Ce at least partly
1-xzr
xo
2mixed oxide forms, wherein x is less than 1 and at least equals 0.01, preferably at least equals 0.02.
4. dispersion as claimed in claim 2, is characterized in that this compound is formula Ce at least partly
1-x-yzr
xsn
yo
2mixed oxide forms, wherein eligible 0.05≤x≤0.95 of x+y<1, x, and y at least equals 0.01, preferably at least equals 0.05.
5. dispersion as claimed in claim 2, is characterized in that this compound is formula Ce at least partly
1-x-yzr
xln
yo
2mixed oxide forms, wherein eligible 0.05≤x≤0.95 of x+y<1, x, and y at least equals 0.01, preferably at least equals 0.02.
6. dispersion as claimed in claim 2, is characterized in that this compound is formula Ce at least partly
1-x-y-zzr
xsn
yln
zo
2mixed oxide forms, wherein eligible 0.05≤x≤0.95 of x+y+z<1, x, y at least equals 0.01, preferably at least equals 0.10, and z at least equals 0.01.
7. dispersion as claimed in claim 1, is characterized in that element M is rare earth metal Ln, more especially trivalent rare earth metals, or the combination of rare earth metal, and this compound is formula Ce at least partly
1-xln
xo
2mixed oxide forms, wherein x equals 0.15 at most and at least equals 0.01, preferably at least equals 0.02.
8. dispersion as claimed in claim 1, is characterized in that element M is titanium and this compound is formula Ce at least partly
1-xti
xo
2mixed oxide forms, wherein x equals 0.6 at most and at least equals 0.01, preferably at least equals 0.05.
9. the dispersion as described in one of claim 5 to 7, is characterized in that rare earth metal Ln is praseodymium.
10. the dispersion as described in one of aforementioned claim, is characterized in that its cerium comprising the amount of 0.005 to 0.05 (III).
11. dispersions as described in one of aforementioned claim, is characterized in that the compound of cerium and other element M of at least one exists with the form of the particle of maximum 10 nanometers of size.
12. dispersions as described in one of aforementioned claim, is characterized in that the compound of cerium and other element M of at least one comprises the particle of citrate anion form with surface exists.
13. dispersions as described in one of claim 1 to 11, it is characterized in that the compound of cerium and other element M of at least one comprises the form existence of the particle of difunctional compound with surface, this difunctional compound comprises the functional group R of amine, sulfuric ester, phenyl, alkyl ethoxy or succinic acid ester type
1with the functional group R of carboxylic acid, dicarboxylic acids, phosphoric acid, phosphonic acids or sulfonic acid type
2, functional group R
1and R
2pass through-(CH
2)
xthe organic chain of-type separates.
14. dispersions as described in one of aforementioned claim, is characterized in that continuous phase is containing aqueous phase.
15. based on the dispersible solid of the compound of other element M of at least one of cerium and selected among zirconium, rare earth metal (Ln), titanium and tin except cerium, this compound is the form of mixed oxide, wherein cerium and element M are solid solution thereof, it is characterized in that it can disperse to provide the dispersion as described in one of aforementioned claim containing in aqueous phase again.
The preparation method of 16. dispersions as described in one of claim 1 to 14, is characterized in that the method comprises the following steps:
-forming the liquid medium comprising the salt of cerium and at least one element M, this cerium salt is the salt of cerium (IV) and cerium (III);
-this medium is contacted with alkali with the pH value obtaining at least 9, obtain sediment thus;
-described sediment is separated with medium;
-wash this sediment;
-by making this sediment peptization with acid treatment, obtain dispersion thus; At least one washing step after the method is included in sediment separating step in addition or after peptization step.
The preparation method of 17. dispersions as claimed in claim 16, the form that wherein compound of cerium and other element M of at least one comprises the particle of citrate anion with surface exists, and it is characterized in that adding citric acid in the dispersion obtained after by sour peptization.
The preparation method of 18. dispersible solids as claimed in claim 15, is characterized in that the method comprises the following steps:
-forming the liquid medium comprising the salt of cerium and at least one element M, this cerium salt is the salt of cerium (IV) and cerium (III);
-this medium is contacted with alkali with the pH value obtaining at least 9, obtain sediment thus;
-described sediment is separated with medium;
-wash this sediment;
-by making this sediment peptization with acid treatment, obtain dispersion thus;
-dispersion by obtaining after sour peptization is evaporated; At least one washing step after the method is included in sediment separating step in addition or after peptization step.
19. methods as described in one of claim 16 to 18, is characterized in that by making sediment peptization by nitric acid, hydrochloric acid or acetic acid treatment.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0503951A FR2884732B1 (en) | 2005-04-20 | 2005-04-20 | COLLOIDAL DISPERSION OF A CERIUM COMPOUND AND ANOTHER ELEMENT SELECTED FROM ZIRCONIUM, RARE EARTHS, TITANIUM AND TIN, DISPERSIBLE SOLID BASED ON THIS COMPOUND AND METHODS OF PREPARATION |
| FR0503951 | 2005-04-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800163214A Division CN101175697A (en) | 2005-04-20 | 2006-04-18 | Colloidal dispersion of a cerium compound and another element selected among zirconium, rare earths, titanium and tin, dispersible solid based on said compound and preparation methods |
Publications (1)
| Publication Number | Publication Date |
|---|---|
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Family
ID=35645859
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| CN201510033691.XA Pending CN104667839A (en) | 2005-04-20 | 2006-04-18 | Colloidal dispersions of compounds of cerium and at least one of zirconium, rare earths, titanium and/or tin, dispersible solid based on said compound, and preparation methods |
| CNA2006800163214A Pending CN101175697A (en) | 2005-04-20 | 2006-04-18 | Colloidal dispersion of a cerium compound and another element selected among zirconium, rare earths, titanium and tin, dispersible solid based on said compound and preparation methods |
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Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20090215614A1 (en) |
| EP (1) | EP1874690A1 (en) |
| JP (1) | JP4954977B2 (en) |
| KR (1) | KR100934560B1 (en) |
| CN (2) | CN104667839A (en) |
| CA (1) | CA2606198C (en) |
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Cited By (1)
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|---|---|---|---|---|
| CN110394171A (en) * | 2018-04-24 | 2019-11-01 | 丰田自动车株式会社 | Hydrogen-storing material and its manufacturing method |
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| US8883865B2 (en) | 2006-09-05 | 2014-11-11 | Cerion Technology, Inc. | Cerium-containing nanoparticles |
| US10435639B2 (en) | 2006-09-05 | 2019-10-08 | Cerion, Llc | Fuel additive containing lattice engineered cerium dioxide nanoparticles |
| WO2008030805A1 (en) | 2006-09-05 | 2008-03-13 | Cerion Technology, Inc. | Cerium dioxide nanoparticle-containing fuel additive |
| FR2933100B1 (en) * | 2008-06-25 | 2010-08-13 | Commissariat Energie Atomique | RUMINESCENT RARE EARTH OXIDE PARTICLE DISPERSIONS, VARNISH COMPRISING THESE PARTICLES, PROCESSES FOR PREPARING THE SAME, AND METHOD FOR MARKING SUBSTRATES. |
| KR101605465B1 (en) * | 2008-12-17 | 2016-03-22 | 세리온, 엘엘씨 | Fuel additive containing lattice engineered cerium dioxide nanoparticles |
| US8530372B2 (en) * | 2009-07-22 | 2013-09-10 | Basf Corporation | Oxygen storage catalyst with decreased ceria reduction temperature |
| US8580701B2 (en) * | 2010-11-19 | 2013-11-12 | Corning Incorporated | Method of controlling Ce:Zr ratio in oxide nanoparticles |
| US10143661B2 (en) | 2013-10-17 | 2018-12-04 | Cerion, Llc | Malic acid stabilized nanoceria particles |
| JP5870081B2 (en) * | 2013-12-13 | 2016-02-24 | セリオン テクノロジー インコーポレイテッド | Lattice engineered cerium dioxide nanoparticles containing fuel additives |
| TW201822886A (en) * | 2014-06-24 | 2018-07-01 | 法商羅地亞經營管理公司 | Metal doped cerium oxide compositions |
| FR3131654B1 (en) * | 2021-12-30 | 2024-01-19 | Commissariat Energie Atomique | METHOD FOR MANUFACTURING A NUCLEAR FUEL IN COMPACTED FORM BASED ON AT LEAST ONE ACTINIDE ELEMENT AND ONE OTHER ELEMENT |
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| US6506705B2 (en) * | 1996-12-06 | 2003-01-14 | Rhodia Chimie | Composition based on cerium oxide or on cerium and zirconium oxides, in the extruded form, process for the preparation thereof and use thereof as catalyst |
| FR2756819B1 (en) * | 1996-12-06 | 1999-02-19 | Rhodia Chimie Sa | COMPOSITION BASED ON CERIUM OXIDE OR CERIUM OXIDES AND ZIRCONIUM, IN EXTRUDED FORM, PROCESS FOR PREPARING SAME AND USE AS CATALYST |
| JP3595874B2 (en) * | 1999-03-05 | 2004-12-02 | 第一稀元素化学工業株式会社 | Zirconium-cerium composite oxide and method for producing the same |
| DE60033328T2 (en) * | 1999-03-05 | 2007-11-22 | Daiichi Kigenso Kagaku Kogyo Co. Ltd. | Mixed oxide based on cerium and zirconium, process for its preparation; the mixed oxide containing catalyst and application of the catalyst for exhaust gas purification |
| FR2803224B1 (en) * | 1999-12-30 | 2002-09-27 | Rhodia Chimie Sa | AQUEOUS COLLOIDAL DISPERSION BASED ON AT LEAST ONE COMPOUND OF A METAL AND A COMPLEXANT, METHOD OF PREPARATION AND USE |
| FR2804102B1 (en) * | 2000-01-26 | 2002-08-16 | Rhodia Terres Rares | AQUEOUS COLLOIDAL DISPERSION OF A CERIUM COMPOUND AND AT LEAST ONE OTHER ELEMENT SELECTED AMONG RARE EARTHS, TRANSITION METALS, ALUMINUM, GALLIUM AND ZIRCONIUM, PROCESS FOR PREPARATION AND USE |
| FR2809637B1 (en) * | 2000-06-05 | 2003-01-24 | Rhodia Terres Rares | COLLOIDAL DISPERSION OF A CERIUM COMPOUND OR A CERIUM COMPOUND AND AT LEAST ONE OTHER ELEMENT SELECTED AMONG RARE EARTHS AND TRANSITION METALS, INCLUDING AN AMINO ACID |
| FR2867769B1 (en) * | 2004-03-17 | 2006-05-05 | Rhodia Chimie Sa | COMPOSITION BASED ON ZIRCONIUM, CERIUM AND TIN OXIDES, PREPARATION AND USE AS CATALYST |
-
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-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110394171A (en) * | 2018-04-24 | 2019-11-01 | 丰田自动车株式会社 | Hydrogen-storing material and its manufacturing method |
| CN110394171B (en) * | 2018-04-24 | 2022-03-29 | 丰田自动车株式会社 | Oxygen storage material and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100934560B1 (en) | 2009-12-29 |
| US20090215614A1 (en) | 2009-08-27 |
| CN101175697A (en) | 2008-05-07 |
| CA2606198C (en) | 2012-07-31 |
| JP2008538349A (en) | 2008-10-23 |
| KR20070122238A (en) | 2007-12-28 |
| WO2006111650A1 (en) | 2006-10-26 |
| FR2884732B1 (en) | 2007-08-24 |
| FR2884732A1 (en) | 2006-10-27 |
| EP1874690A1 (en) | 2008-01-09 |
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| JP4954977B2 (en) | 2012-06-20 |
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